Metallo-thioplasts



Patented Oct. 14, 1952 UNITED STATE-S PATENT OFFICE METALLO-THIOPLASTSLev Akobjanofi, St. Louis, M0.

N Drawing. Application November 16, 1951, Serial No. 256,841

13 Claims.

possess various disadvantages becoming, for instance, porous on heating,and yielding a disagreeable and toxic odor. The metallothioplastics (ormetallothioplasts) of the present invention possess the desirableproperties of the polysulfide plastics together with other advantagesand without the disadvantages just mentioned.

The metallo-thioplastics contain the repeating unit where representsstructure selected from the groups containing two carbon atoms connectedby a valence bond and two carbon atoms separated by and joined tointervening structure, and where represents the residue of the chalcogencontaining compound, in which Z, Z, and Z" are chalcogens and B is anon-reactive nucleus chosen among the metals: Hg, Mo, Sb, Sn, V, W, Zn,known to be the only ones able of forming thio-(seleno-, telluro-) acidssalts of which dissolve in water without being hydrolized; and wherein ais 0 and b is 1 when the valence of B is 2, a is 0 and b is 2 when thevalence of B is 3, a is 1 and b is 1 when the valence of B is 4, a is 1and b is 2 when the valence of B is 5, a is 2 and b is 1 when thevalence of B is 6.

The chalcogen containing compound which may be reacted with adifunctional organic compound may be exemplified by the followingformulas:

l. MZ-B-ZM (valence of B is 2) MZB (valence of B is 3) MZ-l 3 -ZM(valence 0! B is 4) 4. z' ZM MZ-B (valence of B is 5) IIIM MZB-ZM(valence of B is 6) in which M is a member of the group consisting ofalkali and alkaline earth metals, ammonia and amines, specific membersinclude sodium, potassium, lithium, caesium, etc., ammonia,ethanolamines, etc. The preferred substituent is sodium.

The difunctional organic compound may be exemplified as follows:

in which X and X are any substituents which can be split off bytreatment with the alkaline substance M, specific members includinghalogen, acid sulphate, nitrate, acid phosphate, bicarbonate, formate,acetate, propionate, laurate, oleate, stearate, oxalate, acid malonate,acid tartrate, acid citrate, etc. Thus an organic compound having atleast two carbon atoms and a substituent attached to each of the carbonatoms, which substituent is split off during the reactions which occurwhen said compound is treated with a chalcogen compound from the groupdefined above, may be used in producing the plastics of this invention.

The intervening structure between the two carbon atoms may be thefollowing:

. Saturated straight chain hydrocarbons. Saturated branched chainhydrocarbons. Aromatic structure Unsaturated hydrocarbon structure.Ether linkages (including acetals, thioethers,

etc). Members of the ether group include:

C1CsH4OCH2C1, C1C6H4CH2OCH2C6H4C1, and other difunctional ethers.Members of the unsaturated group include: 1,4-dichlorobutene 2;

1,7-dichloroheptene 3; 1,6-dichloroheptene 3; 1.4- d1chloropentene;1,6-dichlorohexene 3; and other difunctional unsaturated carboncompounds.

The reaction of dichloroethylene and sodium polysulfide has been knownsince 1840 when Loe- C] CHgCHCHcCl ClCHiCHzCH C! CH: CH:

wig and Weidemann performed their experiments.

Since then many polysulfide plastics have been synthetized as shown bythe patents to Joseph C. Patrick and others but all of these plasticsare polysulfldes and possess the disadvantages shown above. entinvention were formulated in such a way as to include as non-reactivenucleus elements from groups of the periodic table other than the sulfurfamily. Thus sulfur groups such as:

s s s s s are known to exist in the repeating units of the polysulfideplastics of today and are the cause of the disagreeable odors possessedby these plastics. It has now been discovered that the presence of anon-reactive non-sulfur nucleus these sulfur groups stabilizes thepolysulfides against loss of volatile fragments containing suliur. asshown by the odorless property of these new plastics. Also these newplastics do not have the tendency to blister or become porous when beingprocessed as by molding.

In my copending U. S. patent application Serial No. 63,620, filedDecember 4. 1948, which became U. S. Patent No. 2,587,805 of March 4,1952, the use of the element As as such a nonreactive nucleus is shown.As described below, other elements: Hg, Mo, Sb, Sn, V, W, Zn, are apt tofunction in the same way. Contrary to arsenic these seven elements aremetals; they form a natural group being the only ones known to givethio-(seleno-. telluro-) acids, watersolu ble salts of which are nothydrolized, the stability of these salts being an essential conditionfor their use in condensations to metallo-thioplastics.

The actual atomic grouping of B will depend upon the valence of themetal being used and the conditions of reaction employed in produc ingthe chalcogen containing compound. For example, when sodium sulfide isreacted with zinc sulfide a compound having the following structuralformula is produced: NaS-Zn-S -Na :hich corresponds to the generalformula (number 1 above) in which E is the element zinc, M is sodium, Zand Z is sulfur. In order to produce a chalcogen compound correspondingto the formula None of these plastics prior to the pres- 4 (number 2above) sodium sulfide and antimo nious sulfide (SbzSz) are reactedtogether to produce the compound SNa NaSSb SNs A compound correspondingto the formula MZBZ"M (number 3 above) is prepared by reaction of sodiumsulfide with tin disulfide ($1182) to yield the substance NaSSn-SNa Acompound corresponding to the formula MZB (number 4 above) is preparedby reaction of sodium disulfide vith vanadium pentasulfide (V255) togive A compound corresponding to the formula 2 m de-2nd (number 5 above)is prepared by reacting sodium sulfide with ammonium molybdate(NH4)5M07O24 to produce the compound s XcS-lllo-Sl\'e '5' Thus it may beseen that in the production of the plastics of this invention thechalcogen atoms are bound together chemically by the nonreactivemetallic nucleus B. Compounds have been produced in which B has thevalue:

.Hg. (orl ip) .Sb:

.Zn. y y

Some of the salts of the above metals represented by B are prepared asfollows:

Another important characteristic of these salts is their ability toreadily react with difunctional organic compounds. The reaction of thesesalts with the organic compounds is carried out in a solvent mediumwhere the compounds are mutually soluble. For work in aqueous medium,the organic substances may be emulsified or in a molten state. Forexample, the solutions may correspond to the use of a /5 gram molecularweight. The organic compound such as dichloroethylene may be added in aslight molecular excess and the mixture may be heated progressively.

The sulfomercuriates, molybdates, vanadates, tungstates and zincatesreact with the organic compound x-ci: (IE-X readily at room temperature,and more quickly (30 minutes to 1 hour) when the mixture is boiled. Athick precipitate forms as the reaction takes place. Thesulfoantimonates react energetically, for example, withdichloroethylene. The poly mers formed are of a yellowish-white color.The reaction of the sulfostannates is complete, for example, afterheating for some 15 hours at 120 C. if treated under pressure. Theproducts of reaction can be filtered, washed with water and dried inair.

Compounds of the type Z--B-Z and are thermoplastic, softening attemperatures of 150 C. to 180 C.; for the type containing Sbthermoplasticity at about 100 C. is observed, also brownishdiscoloration of the originally yellowish-White plastic; Hg containingmetallo-thioplasts soften only slightly on heating as high as 240-250 C.The softening point of presentl known polysulfide plastics is 75 C.

The solubility of these products in organic solvents depends on theorganic material used in their preparation.

The following examples illustrate the manner of making the compounds andthe conditions under which these compounds are reacted with thedifunctional organic compounds I (ll-X- to produce the plastics or thisinvention. All parts are in weight unless otherwise indicated.

Example 1 A compound containing the nucleus Hgwas prepared by reacting15 parts of mercuric sulfide (HgS) with 7.8 parts of sodium sulfide in35 parts by volume of water. A colorless solution containing thecompound sodium sulfomercuriate was formed (NaSz) Hg. A modified plastichaving the general formula (SHgSR) was prepared by reacting 19.5 partsof sodium sulfomercuriate with parts of ethylene dichloride and 30 partsof water at a temperature of 20 C. for A hour and then at a temperatureof 84 C. for 1 hour. The resulting resin was a white powder,substantially odorless, sublimated at a temperature above 240 C.,soluble in acetone, benzene, and carbon disulfide, and insoluble innaphtha.

Example 2 A compound containing the nucleus Znwas prepared by reacting12 parts of zinic sulfide ZnS with 7.8 parts of sodium sulfide in 50parts of water. A viscous colorless solution was formed containing thecompound sodium sulfozincate (NaS)zZn. A modified plastic having thegeneral formula (-SZHSRr-)y was prepared by reacting 17.5 parts of(NaS)zZn with 10 parts of ethylene dichloride and 45 parts of water at25 C. for /2 hour and then at 84 C. for 1 hour. The resulting resin waswhite, odorless, melted at 184 C., soluble in acetone, benzene andnaphtha, insoluble in carbon disulfide.

A further reaction was carried out in which 15 parts of O(C2H4)2Cla wasreacted with 17.5 parts of (NaS)2Zn and 45 parts of water at 84 C. for 6hours. The resulting material was a yellowish oil of medium viscosity,odorless at room temperature and having a very weak aromatic odor whenwarmed; soluble in benzene, acetone. diethylether and insoluble in CS2and naphtha.

Example 3 A compound containing the nucleus Zn-- was prepared byreacting 20 parts of ZnS with 14 parts of KOH dissolved in 30 parts ofwater, the resulting filtered solution contained a compound having thecomposition potassium sulfoxyzincate Zn(SK) (OK). A composition havingthe general formula HOZnSR was prepared by reacting 19 parts of KOZnSKwith 10 parts of ethylene dichloride and 30 parts of water at 84 C. for8 hours. The resulting material was a white dry powder which carbonizedat a temperature of 240 C.; very slightly soluble in CS2, naphtha, andacetone, and insoluble in benzene.

Example 4 A compound having the nucleus -Sn(S)- was prepared by reactinga mixture of 7.8 parts of News and 18 parts of SnS-z, for which purposeboth salts were molten together. SnSz has been prepared by reacting astannic salt in aqueous solution with 1128 and extracting the resultingmixture with acetone to eliminate the free sulfur. The resultingcompound was Na sulfostannate NazSnSa. A modified plastic having thegeneral formula (SSn(S)SR)v was prepared by reacting 522 parts ofNazsnsz with 20 parts of ethylene dichloride and 180 parts of water atC. for 15 hours. The resultin resin was elastic and workable on a rubbermill, thermoplastic at approximately C., soluble in carbon disulfide andinsoluble in benzene.

Example 5 A compound containing the nucleus Sb(S)- was prepared byreacting 7.8 parts of NazS with 41 parts of SbzSs. The resulting productwas sodium sulfoantimonate NazSbSa. A modified plastic having thegeneral formula was prepared by reacting 64 parts of NaaSbSr with 30parts of ethylene dichloride in the presence of parts of water at 84 C.The reaction was completed very rapidly. ..The resulting product wasyellow at first and turning brown 7 in color; workable on the rubbermill, thermoplastic at 100 C., soluble in carbon disulflde and insolublein benzene.

Example 6 A compound containing the nucleus V(S) was prepared byreacting 7.8 parts of NazS in 25 parts of water with 12 parts of NH4VO3in 450 parts of water. The resulting product was sodium sulfovanadateNaaVSi. A modified or metallo-thioplastic having the general formulaExample 7 A compound containing the nucleus was prepared by reacting31.2 parts of NazS in 50 parts of water with parts of (NH4)6M01O24 in100 parts of water. The resulting product was sodium sulfomolybdateNa2MoS4. thioplastic having the general formula (SMo(S) 2SR) 1 wasprepared by reacting 45 parts of Nt2MOs4 and parts of ethylenedichloride and 300 parts of water at 84 C. for minutes. The resultingproduct was white odorless, melting at 178 C., soluble in CS2, naphtha,benzene, insoluble in acetone.

Example 8 A compound containing the nucleus .W(S)2- was prepared byreacting 31.2 parts of NazS in 20 parts of water with 30 parts of Na2WO4in 100 parts of water. The resulting product was sodium sulfotungstateNazWSr. A modified plastic having the general formula l--SW(S)2SR-)y wasprepared by reacting 62.5 parts of Na2WS4 with 20 parts of ethylenedichloride in the presence of 240 parts of water at 84 C. for 30minutes. The resulting product was white, odorless, melting at 130 C.,soluble in benzene, CS2, and acetone, insoluble in naphtha.

A further reaction was carried out in which 30 parts of O(C-. H4Ci)2 wasreacted with 62.5 parts of NazWSi in the presence of 240 parts of waterat 84 C. for 24 hours. The resulting oily product was colorless,odorless, and soluble in benzene, acetone, and carbon disulfide.

The above reaction can also be carried out with monofunctional organiccompounds. The obtained products are monomeric esters of the chalcoacidsFhe metailo-thioplasts obtained by the various processes described areprocessed in a manner similar to that used in the treatment of ordinarypolysulfides. In particular treated b the proc=':edlhgs established forrubber and other plastic; The compounding of the modifiedmetallothioplastics may follow the same lines as the COlflDOlllzdlIlg ofordinary polysulfides.

A metallo- Particularly interesting is the treatment with sulfur. Sulfursublimes even more readily than the ordinary polysulfides but as far asodor is concerned, the effect of sulfur vapors is practicallynon-existent, contrary to known polysulfides especially those having theformula -C:H4.S4-, which produce a violent physiological reaction. Ithas been found in the course of this work that mixtures of polysulfideswith sulfur are plasticized by simple heating to temperatures rangingfrom C. to C. Modified polysulfldes and particularly themetallothioplastics show this effect to the same extent as the others.Products so prepared are similar to vulcanized polysulfldes by all theiressential criteria. In principle there is no limit to the quantities ofsulfur that may be added but sulfur in amounts of 300% and more requiresthe addition of stabilizing substances in order to avoid ageing.

Another interesting effect is obtained by blending modified polysulfidesand particularly metallo-thioplastics with ordinary polysulfides. Theresulting blend is less volatile than the ordinary polysulfide.

This application is a continuation in part of my application Serial No.63,620 of December 4, 1948.

While certain representative embodiments and details have been shown forthe purpose of iilustrating the invention, it will be apparent to thoseskilled in the art that various changes and modifications may be madetherein without dein which --C C- represents structure selected from thegroup consisting of two adjacent carbon atoms connected by a valencebond and two carbon atoms separated by and joined to interveningstructure; Z, Z and Z" are chalcogens of atomic number greater than 8; Bis a nonreactive nucleus chosen from the group of metals consisting of:Hg, Mo, Sb, Sn, V, W, Zn; and wherein a is 0 and b is 1 when the valenceof B is 2, a is 0 and b is 2 when the valence of B is 3, a is 1 and b is1 when the valence of B is 4, a is l and b is 2 when the valence of B is5, a is 2 and b is 1 when the valence of B is 6.

2. A polymeric substance having the repeating unit -0 C-ZHg-Z) in whichC C represents structure selected from the group consisting of twoadjacent carbon atoms connected by a valence bond and two carbon atomsseparated by and joined by intervening structure; and wherein Z, Z andZ" are chalcogens of atomis number greater than 8.

3. A polymeric substance having the repeating unit in which C C-represents structure selectedfrom the group consisting of two adjacentcarbon atoms connected by a valence bond and two carbon atoms separatedby and joined to intervening structure.

4. A polymeric substance having the repeating unit 2 CZ'MoZ'-) in whichC 0- represents structure selected from the group consisting of twoadjacent carbon atoms connected by a valence bond and two carbon atomsseparated by and joined to intervening structure; and wherein Z, Z, Z"and Z are chalcogens of atomic number greater than 8. 5. A polymericsubstance having the repeating unit in which -C C-- represents structureselected from the group consisting of two adjacent carbon atomsconnected by a valence bond and two carbon atoms separated by and joinedto intervening structure.

6. A polymeric substance having the repeating unit (-C C-Z-Sb:(Z')z) inwhich -C C represents structure selected from the group consisting oftwo adjacent carbon atoms connected by a valence bond and two carbonatoms separated by and joined to intervening structure; and wherein Zand Z are chalco gens of atomic number greater than 8.

7. A polymeric substance having the repeating unit (C CS-Sb:(S-)z) inwhich C C- represents structure selected from the group consisting oftwo adjacent carbon atoms connected by a valence bond and two carbonatoms separated by and joined to intervening structure.

8. A polymeric substance having the repeating unit in which -C C-represents structure selected from the group consisting of two adjacentcarbon atoms connected by a valence bond and two carbon atoms separatedby and joined to intervening structure. and wherein Z,. Z and Z" arechalcogens of atomic number greater than 8.

10 9. A polymeric substance having the repeating unit in which --C 0-represents structure selected from the group consisting of two adjacentcarbon atoms connected by a valence bond and two carbon atoms separatedby and joined to intervening structure.

10. A polymeric substance having the repeating unit in which -0 C-represents structure selected from the group consisting of two adjacentcarbon atoms connected by a valence bond and two carbon atoms separatedby and joined to intervening structure; and wherein Z, Z and Z" arechalcogens of atomic number greater than 8.

11. A polymeric substance having the repeat ing unit in which C Crepresents structure selected from the group consisting of two adjacentcarbon atoms connected by a valence bond and two carbon atoms separatedby and joined to intervening structure.

12. A polymeric substance having the repeating unit (-0 CZZnZ) in which-C C represents structure selected from the group consisting of twoadjacent carbon atoms connected by a valence bond and two carbon atomsseparated by and joined to intervening structure; and wherein Z and Zare chalcogens of atomic number greater than 8.

13. A polymeric substance having the repeating unit (-0 C-SZn-S) inwhich C C represents structure selected from the group consisting of twoadjacent carbon atoms connected by a valence bond and two car bon atomsseparated by and joined to intervening structure.

LEV AKOBJANOFF.

No references cited.

1. A POLYMERIC SUBSTANCE HAVING THE REPEATING UNIT